Article
Chemistry, Multidisciplinary
Hong Deng, Minyan Wang, Yong Liang, Xiangyang Chen, Tianhang Wang, Jonathan J. Wong, Yue Zhao, Kendall N. Houk, Zhuangzhi Shi
Summary: Phosphorous-containing heterocycles exhibit markedly different properties than common heterocyclic compounds, but the lack of synthetic methods has made the study of these molecules difficult, especially in terms of constructing P-stereogenic centers. This research presents a simple, versatile method for synthesizing PN-heterocycles with P(V) centers from phosphanamines through palladium catalyzed intramolecular C-P coupling.
Article
Chemistry, Inorganic & Nuclear
M. Angeles Alvarez, M. Esther Garcia, Daniel Garcia-Vivo, Miguel A. Ruiz, Patricia Vega
Summary: Phosphanyl complexes were synthesized through photolysis and reactions, and heterometallic bridged derivatives were prepared using various synthetic strategies. The yields of products obtained from photochemical reactions were low, but higher yields were achieved through reactions with halide complexes. The obtained derivatives exhibit important chemical properties and are valuable for further research.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Physical
Catherine A. Moulder, Kristina Kafle, Christopher X. Zhou, Thomas R. Cundari
Summary: This research focuses on predicting the BDEs of WE(E = Si, P, and S) bonds and assessing the uncertainty of these predictions. It highlights issues with underestimation in pi-bond strengths using certain density functional theory methods and demonstrates challenges with using perturbation theory methods for fragments derived from W-P homolysis. Despite the broad standard deviations observed in modeling metal thermochemistry with DFT and MP2 levels of theory, the average BDEs found using various methods are reliable.
JOURNAL OF PHYSICAL CHEMISTRY A
(2021)
Article
Chemistry, Inorganic & Nuclear
Isabel G. Albuerne, M. Angeles Alvarez, M. Esther Garcia, Miguel A. Ruiz, Patricia Vega
Summary: The study involved the in situ preparation of a new pyramidal phosphinidene-bridged complex and the unexpected Michaelis-Arbuzov-like rearrangement upon dissolution. Reactions with different internal and terminal alkynes showed rapid and highly regioselective formation of metallacyclic products at room temperature.
INORGANICA CHIMICA ACTA
(2021)
Review
Chemistry, Multidisciplinary
Jingzhen Du, Philip J. Cobb, Junru Ding, David P. Mills, Stephen T. Liddle
Summary: This article reviews the complexes containing chemical bonds between f-elements and heavy pnictogens from phosphorus to bismuth. It emphasizes the achievements that have been made in this emerging field, as well as the remaining work to be done.
Article
Chemistry, Inorganic & Nuclear
Callum Branfoot, Paul G. Pringle, Natalie E. Pridmore, Tom A. Young, Duncan F. Wass
Summary: This study investigates the reactions of R2P-PR2 with R'E-ER' and explores the mechanism experimentally and computationally. It is found that the reactions can efficiently synthesize R2P-ER' under specific conditions. The addition of TEMPO radical scavenger is shown to inhibit the reaction, suggesting the involvement of radicals in the reaction mechanism. Furthermore, the study reveals the influence of different chalcogen elements (S, Se, O, Te) on the reaction through experiments and calculations, providing a theoretical basis for further design and optimization of the reaction.
DALTON TRANSACTIONS
(2022)
Article
Chemistry, Inorganic & Nuclear
Shuruthi Senthil, Michael R. Gau, Daniel J. Mindiola
Summary: The complex [(BDI)VCl(N{SiMe3}2)] can be reduced with Na/NaCl in the presence of white P4 to form a dinuclear species [(BDI)V(N{SiMe3}2)]2(mu-eta 1:eta 1-P6), which features a chairlike tricyclic [P6]2- scaffold bridging two V centers. The structures of complexes 1 and 2 have been characterized, and a formation pathway for the chairlike tricyclic [P6]2- scaffold in 2 is proposed.
Article
Chemistry, Organic
Hyung Yoon, Alexandra Galls, Soren D. Rozema, Scott J. Miller
Summary: Enantioselective Cu-catalyzed C-O cross coupling reactions have been developed to yield atropisomeric resorcinol-bearing quinazolinones. By using a new guanidinylated dimeric peptidic ligand, the desired products were obtained with good yields and excellent stereocontrol. The reaction was easily scalable and various product derivatizations were carried out.
Article
Chemistry, Inorganic & Nuclear
Ritu Yadav, Bindusagar Das, Ashi Singh, Ankita Anmol, Ankita Sharma, Chinmoy Majumder
Summary: This study reports the synthesis and characterization of BICAAC-stabilized phosphinidenes. X-ray crystallography and NMR spectroscopy were used to characterize the compounds, and theoretical calculations indicated the presence of characteristic double bonds.
DALTON TRANSACTIONS
(2023)
Article
Chemistry, Inorganic & Nuclear
Ritu Yadav, Bindusagar Das, Ashi Singh, Ankita Anmol, Ankita Sharma, Chinmoy Majumder
Summary: In this study, the synthesis and characterization of bicyclic (alkyl)(amino)carbene (BICAAC)-stabilized phosphinidenes were reported. The compounds were obtained through reactions between trihalophosphine and BICAAC, and their structures were confirmed by X-ray crystallography and NMR spectroscopy. Theoretical calculations revealed the presence of predominant C(carbene)-P double bond characteristic in these compounds.
DALTON TRANSACTIONS
(2023)
Review
Chemistry, Multidisciplinary
Chongqing Pan, Zhenhua Gu
Summary: Atropisomerism is a prominent stereochemical behavior arising from restricted rotation, and it has been widely applied in bioactive substances, catalysts, and materials science. Transition-metal-catalyzed asymmetric carbene transformation reactions provide an effective strategy to achieve extraordinary stereocontrol in atropisomers.
TRENDS IN CHEMISTRY
(2023)
Article
Chemistry, Organic
Christopher J. Douglas, Steven J. Underwood
Summary: This article presents a method for rhodium-catalyzed C-O bond functionalization of N-pyridylimidates using a recyclable and traceless amine directing group. In addition to discussing the substrate scope, it also explores the behavior of this class of compounds and how it affects their reactivity.
Article
Chemistry, Multidisciplinary
Malte Fischer, Fabian Reiss, Christian Hering-Junghans
Summary: The titanocene complexes with terminal phosphinidene or arsinidene ligands were synthesized using phospha-Wittig reagent and arsa-Wittig reagent, showing singlet biradicaloid characteristics in their ground state according to ab initio studies.
CHEMICAL COMMUNICATIONS
(2021)
Article
Biochemistry & Molecular Biology
Giulio Bresciani, Stefano Zacchini, Guido Pampaloni, Marco Bortoluzzi, Fabio Marchetti
Summary: Diiron mu-aminocarbyne complexes can be synthesized by reacting sodium cyanate and tetrabutylammonium thiocyanate with pre-prepared diiron aminocarbyne complexes, yielding different substituted diiron cyanide complexes with yields of 67-81%, through substitution of the acetonitrile ligand. When reacted with potassium selenocyanate at reflux temperature, cyanide complexes can be obtained with yields of 45-67%. When reacted at room temperature in acetone, a small amount of potassium selenocyanate complexes can be obtained. All products were fully characterized and the chiral structure was determined by single crystal X-ray diffraction. DFT calculations shed light on the coordination mode and stability of the {NCSe-} fragment.
Article
Chemistry, Multidisciplinary
Eric S. S. Yang, Daniel W. N. Wilson, Jose M. M. Goicoechea
Summary: The cyaphide anion, CP-, can undergo three different oligomerization reactions in the coordination sphere of metals. These reactions result in the formation of tetra-metallic, asymmetric bimetallic, and trimetallic complexes containing various phosphorus-containing fragments. The study highlights the instability of cyaphido transition metal complexes towards further oligomerization processes.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
M. Angeles Alvarez, Melodie Casado-Ruano, M. Esther Garcia, Daniel Garcia-Vivo, Miguel A. Ruiz
Summary: The unsaturated dicarbonyl complex [Mo 2 Cp 2 ( mu-CH 3 )( mu-P t Bu 2 )(CO) 2 ] reacted with [W(CO) 6 ] under photolytic conditions to give three isomers, with the cis isomers being thermally unstable.
JOURNAL OF ORGANOMETALLIC CHEMISTRY
(2022)
Article
Chemistry, Inorganic & Nuclear
M. Angeles Alvarez, M. Esther Garcia, Daniel Garcia-Vivo, Miguel A. Ruiz, Patricia Vega
Summary: The reactions of [MoReCp(mu-PR*)(CO)(6)] with S-8 are influenced by experimental conditions. Under certain conditions, a novel coordination mode of the thiophosphinidene ligand was observed, where it bridges the dimetal center. Depending on the reaction conditions, the thiophosphinidene ligand can rearrange into different coordination modes, and addition of sulfur atoms can lead to the formation of complexes with novel coordination modes of their ligands. Similar observations were made for reactions with gray selenium.
INORGANIC CHEMISTRY
(2023)
Article
Chemistry, Inorganic & Nuclear
M. Angeles Alvarez, M. Esther Garcia, Daniel Garcia-Vivo, Miguel A. Ruiz, Patricia Vega
Summary: The reactions of [MoReCp(& mu;-PMes*)(CO)(6)] with internal alkynes resulted in the formation of phosphapropenylidene-bridged complexes. The presence of steric repulsions during the reaction led to the formation of different isomers. Similar reactions were observed for [MoMnCp(& mu;-PMes*)(CO)(6)]. Addition of ligands promoted rearrangement of the phosphapropenylidene ligand. The reaction of the MoRe phosphinidene complex with S C NPh produced phosphametallacyclic and thiophosphinidene-bridged isomers.
Article
Chemistry, Inorganic & Nuclear
M. Angeles Alvarez, M. Esther Garcia, Daniel Garcia-Vivo, Miguel A. Ruiz, Patricia Vega
Summary: Complex reactions of [MoMCp(μ-PMes*)(CO)(6)] with H-2 and several p-block element (E) hydrides, resulting in the cleavage of E-H bonds. Different products can be obtained by varying reaction conditions and introducing different ligands.
Article
Chemistry, Inorganic & Nuclear
M. Angeles Alvarez, M. Esther Garcia, Daniel Garcia-Vivo, Miguel A. Ruiz, Patricia Vega
Summary: Heterometallic phosphinidene complexes with high reactivity are useful for constructing novel organophosphorus ligands. The reactions of these complexes with different isocyanides depend strongly on experimental conditions and the size of the substituent.